Dissociation of individual molecules with electrons from the tip of a scanning tunneling microscope

The scanning tunneling microscope (STM) can be used to select a particular adsorbed molecule, probe its electronic structure, dissociate the molecule by using electrons from the STM tip, and then examine the dissociation products. These capabilities are demonstrated for decaborane(14) (B(10)H(14)) molecules adsorbed on a silicon(111)-(7 x 7) surface. In addition to basic studies, such selective dissociation processes can be used in a variety of applications to control surface chemistry on the molecular scale.     

Oscillatory kinetics and spatio-temporal self-organization in reactions at solid surfaces

Chemical reactions far from equilibrium on solid surfaces may exhibit typical phenomena of nonlinear dynamics, as exemplified by the catalytic oxidation of carbon monoxide on a platinum(110) single-crystal surface. Depending on the external parameters (temperature and partial pressures of the reactants), the temporal variation of the reaction rate may become oscillatory or even chaotic. In a parallel way, the concentration distributions of the adsorbed species on the surface form spatio-temporal patterns including propagating and standing waves, rotating spirals, as well as irregular and rapidly changing structures denoted "chemical turbulence."     

Nanoscale imaging of molecular adsorption

In situ atomic force microscope observations were made of the adsorption of anions (1- or 2-) of the organic diacid 5-benzoyl-4-hydroxy-2-methoxybenzenesulfonic acid from aqueous solution onto the (0001) surface of hydrotalcite (HT), a layered clay. This adsorption process is believed to mimic the ion-exchange reactions that occur within the layers of HT and other layered clays. Atomic force microscope images of the (0001) surfaces of HT, acquired in aqueous solutions, reveal an ordered structure with respect to magnesium and aluminum atoms. In the presence of the anions, atomic force microscopy indicates pH-dependent adsorption onto the formally cationic HT surface. The anion coverage is governed by electroneutrality and steric interactions between the bulky anions within the adsorbed layer, whereas the orientation of the anions with respect to the HT surface is dictated by coulombic interactions and hydrogen bonding between the anion's sulfonate moiety and clay hydroxyl triads. These observations reveal that the reversible adsorption of molecular species can be examined directly by in situ atomic force microscopy, providing details of surface stoichiometry and adlayer symmetry on the local, molecular level.     

不同覆盖条件下坡面流水力学特征试验研究

目的坡面流水力学特性对阐明土壤侵蚀和坡面产沙机理具有重要意义,本试验就不同覆盖条件下坡面的坡面流阻力及相关水力学特征进行了研究,探究不同覆盖条件下坡面流水力学特征,以期为指导水土保持坡面措施合理配置提供理论支持。方法试验使用自制定床冲刷水槽,选用不同覆盖度（0%、10%、15%、20%）砾石、草被床面,在不同流量（15 ~ 120 L/（min·m））、不同坡度（3° ~ 15°）条件下进行室内定床冲刷试验。结果结果表明:（1）不同坡面上流速随着流量、坡度的增大而增大,且相同覆盖度下草被床面流速大于砾石床面流速,最高可达其2.2倍。（2）不同覆盖条件下弗劳德数（Fr）随着坡度的增大而增大,Darcy-weisbach阻力系数（f）随着覆盖度的增加而增加,相同覆盖度下砾石床面f大于草被床面,最高可分别为草被床面的10.9倍。（3）不同覆盖条件下坡面流阻力与流量呈线性正相关关系,相同覆盖度下砾石床面坡面流阻力大于草被床面,最高可达草被床面的2.2倍。（4）坡度与覆盖度对坡面流阻力均有显著影响,坡面流阻力随坡度的增大而增大,随着覆盖度的增大而增大,且呈较好的线性相关关系。结论本试验通过对不同覆盖条件下坡面流阻力的研究,可为建立基于径流动力学过程的山坡水文模型和侵蚀物理模型提供一定基础,为指导水土保持坡面措施合理配置提供理论支持。      

Conical intersection dynamics in NO2 probed by homodyne high-harmonic spectroscopy

Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways.     

草地覆盖对伊犁河谷地表产流产沙的影响因素分析

伊犁河谷作为新疆水土流失较为严重的地区之一,探讨如何在此生态环境脆弱区利用植被进行水土保持工作至关重要。采用野外人工模拟降雨的方法,选择不同植被覆盖度的小区(80%、60%、40%、20%、10%、0%),从覆盖度与地表径流速率,以其与径流含沙量之间的定量关系出发进行试验。结果表明,随着植被覆盖度的增加,径流系数变小,径流速率和径流含沙量明显降低。同时,40%植被覆盖度可以作为该区域一个参考的临界值,即植被覆盖度达到这个点时,就可以有效地对该区域进行水土保持。     

Chemistry. Toward vibrational mode control in catalysis

Vibrational excitations of specific bonds in molecules have been used to enhance the reactivity of the molecules in direct gas-phase reactions. In his Perspective, Luntz highlights a report by Beck et al., who show that such vibrational control may also be possible for catalytic reactions at a surface. The authors demonstrate that differently excited deuterated methane molecules have different dissociation probabilities on a nickel surface, even though the energies of the different molecules are similar.     

Ultrafast x-ray diffraction of transient molecular structures in solution

We report direct structural evidence of the bridged radical (CH2ICH2.) in a polar solution, obtained using time-resolved liquid-phase x-ray diffraction. This transient intermediate has long been hypothesized to explain stereo-chemical control in many association and/or dissociation reactions involving haloalkanes. Ultrashort optical pulses were used to dissociate an iodine atom from the haloethane molecule (C2H4I2) dissolved in methanol, and the diffraction of picosecond x-ray pulses from a synchrotron supports the following structural dynamics, with approximately 0.01 angstrom spatial resolution and approximately 100 picosecond time resolution: The loss of one iodine atom from C2H4I2 leads to the C-I-C triangular geometry of CH2ICH2.. This transient C2H4I then binds to an iodine atom to form a new species, the C2H4I-I isomer, which eventually decays into C2H4 + I2. Solvent dynamics were also extracted from the data, revealing a change in the solvent cage geometry, heating, and thermal expansion.     

Reversible control of hydrogenation of a single molecule

Low-temperature scanning tunneling microscopy was used to selectively break the N-H bond of a methylaminocarbyne (CNHCH3) molecule on a Pt(111) surface at 4.7 kelvin, leaving the C-H bonds intact, to form an adsorbed methylisocyanide molecule (CNCH3). The methylisocyanide product was identified through comparison of its vibrational spectrum with that of directly adsorbed methylisocyanide as measured with inelastic electron tunneling spectroscopy. The CNHCH3 could be regenerated in situ by exposure to hydrogen at room temperature. The combination of tip-induced dehydrogenation with thermodynamically driven hydrogenation allows a completely reversible chemical cycle to be established at the single-molecule level in this system. By tailoring the pulse conditions, irreversible dissociation entailing cleavage of both the C-H and N-H bonds can also be demonstrated.     

Time-resolved photoacoustic calorimetry: probing the energetics and dynamics of fast chemical and biochemical reactions

Time-resolved photoacoustic calorimetry is a new experimental technique that measures the dynamics of enthalpy changes on the time scale of nanoseconds to microseconds for reactions initiated by absorption of light. When the reaction is carried out in water, it is also possible to obtain the dynamics of the corresponding volume changes. This method has been applied to a variety of biochemical, organic, and organometallic reactions.     

Autoionization in liquid water

The dissociation of a water molecule in liquid water is the fundamental event in acid-base chemistry, determining the pH of water. Because of the short time scales and microscopic length scales involved, the dynamics of this autoionization have not been directly probed by experiment. Here, the autoionization mechanism is revealed by sampling and analyzing ab initio molecular dynamics trajectories. We identify the rare fluctuations in solvation energies that destabilize an oxygen-hydrogen bond. Through the transfer of protons along a hydrogen bond "wire," the nascent ions separate by three or more neighbors. If the hydrogen bond wire connecting the two ions is subsequently broken, a metastable charge-separated state is visited. The ions may then diffuse to large separations. If, however, the hydrogen bond wire remains unbroken, the ions recombine rapidly. Because of their concomitant large electric fields, the transient ionic species produced in this case may provide an experimentally detectable signal of the dynamics we report.     

松辽流域山地丘陵地区水蚀规律

通过对松辽流域山地丘陵地区水蚀图斑的调查,运用线性模型理论,研究了该流域山地丘陵地区水蚀灾害的影响因素,分析了流域内下垫面诸因素对土壤水蚀量的影响程度,并找出了其主导因素。研究结果表明:在影响土壤水蚀量下垫面的诸因子中,母岩特征、土壤类型、地貌类型、坡度、植被覆盖度与水蚀灾害的关系达显著水平,其中植被覆盖度及坡度是最显著的影响因子,起着主导作用。防止土壤水蚀应以生物措施为主,增加植被覆盖度是最有效的措施。坡度也是影响水蚀的关键因子,受人为活动影响较大的平原、台地、丘陵及低山区,应是防治土壤水蚀的重点地区。     

Dynamics of water molecules in aqueous solvation shells

We report on the direct measurement of the dynamics of water molecules in the solvation shell of an ion in aqueous solution. The hydrogen-bond dynamics of water molecules solvating a Cl-, Br-, or I- anion is slow compared with neat liquid water, indicating that the aqueous solvation shells of these ions are rigid. This rigidity can play an important role in the overall dynamics of chemical reactions in aqueous solution. The experiments were performed with femtosecond midinfrared nonlinear spectroscopy, because this technique allows the spectral response of the water molecules in the solvation shell to be distinguished clearly from that of the other water molecules in the solution.     

Enhancing hydrogen evolution activity in water splitting by tailoring Li⁺-Ni(OH)₂-Pt interfaces

Improving the sluggish kinetics for the electrochemical reduction of water to molecular hydrogen in alkaline environments is one key to reducing the high overpotentials and associated energy losses in water-alkali and chlor-alkali electrolyzers. We found that a controlled arrangement of nanometer-scale Ni(OH)(2) clusters on platinum electrode surfaces manifests a factor of 8 activity increase in catalyzing the hydrogen evolution reaction relative to state-of-the-art metal and metal-oxide catalysts. In a bifunctional effect, the edges of the Ni(OH)(2) clusters promoted the dissociation of water and the production of hydrogen intermediates that then adsorbed on the nearby Pt surfaces and recombined into molecular hydrogen. The generation of these hydrogen intermediates could be further enhanced via Li(+)-induced destabilization of the HO-H bond, resulting in a factor of 10 total increase in activity.     

Rotational coherence and a sudden breakdown in linear response seen in room-temperature liquids

Highly energized molecules normally are rapidly equilibrated by a solvent; this finding is central to the conventional (linear-response) view of how chemical reactions occur in solution. However, when a reaction initiated by 33-femtosecond deep ultraviolet laser pulses is used to eject highly rotationally excited diatomic molecules into alcohols and water, rotational coherence persists for many rotational periods despite the solvent. Molecular dynamics simulations trace this slow development of molecular-scale friction to a clearly identifiable molecular event: an abrupt liquid-structure change triggered by the rapid rotation. This example shows that molecular relaxation can sometimes switch from linear to nonlinear response.     

福建长汀红壤区植被覆盖度变化趋势分析

福建长汀位于中国南方亚热带红壤丘陵区,水土流失、山体滑坡等自然灾害较为严重,分析当地植被覆盖度的变化趋势是评价水土流失治理及生态环境恢复的有效手段。以Landsat数据为基础,应用地理信息系统（ GIS）技术,提取福建省长汀红壤区2000－2014年的归一化植被指数（ NDVI）值,并采用像元二分模型和差值法分别对植被覆盖度、植被恢复等级进行估算。结果表明,15 a长汀红壤区NDVI呈明显上升趋势,植被覆盖度呈明显增加趋势,高植被覆盖面积增加了2132．90 km2,面积比例提高68．86％,植被变化以恢复和完全恢复为主,占全区总面积的88．07％。经过多年的治理,长汀红壤区植被覆盖状况已得到很大改善,但仍有占长汀土地总面积0．42％的区域属植被严重退化区,主要分布于汀江两岸,建议在该流域加强水土流失治理保护措施,合理生产开发利用,从而有效防治水土流失。     

旱作农业区不同田间集雨措施应用效果研究

分别对冬小麦和夏玉米进行了不同田间集雨措施的试验研究。结果表明,起垄可使垄背土壤变得疏松,孔隙度增大,有利于土壤通气透水,增加土壤水库容。这有利于作物根系生长,增强抗倒伏能力,并可以减少地表径流使表土土壤结构体免遭破坏。因土壤贮水能力增加、地形对降水的再分配、土壤水的运移及蒸发强度的不同,使更多水分可以被作物利用。秸秆覆盖也可以缓冲雨滴的冲击力而减弱对土壤结构体的破坏,并且可以减少土壤水的蒸发损失。冬小麦生育期由于降水较少且强度不大,田间地形对降水的再分配效果不明显;而在没有覆盖措施的情况下因加快了土壤水分的蒸发,会降低冬小麦降水利用率。垄沟种植对夏玉米有明显的增产效应,而覆盖的效应相对较小。     

Dangling bond dynamics on the silicon (100)-2x1 surface: dissociation, diffusion, and recombination

The dynamics of dangling bond (DB) diffusion was studied after deuterium desorption from the silicon (100)-2x1 surface. At elevated temperatures, paired DB sites produced after desorption unpaired as deuterium atoms hopped from adjacent dimers. Below 620 kelvin, the unpaired configuration most commonly observed corresponded to two DBs on adjacent silicon dimers. At higher temperatures, unpaired DBs executed one-dimensional walks along the dimer rows, and recombination was observed with the same partner after walks lasting many minutes. The frequency and extent of these excursions increased with temperature. Above 660 kelvin, complete dissociation was observed and was sometimes followed by recombination by means of partner exchange. The implications for low-temperature materials growth are discussed.     

保护性耕作条件下影响蒸发量因素的试验研究

为分析保护性耕作条件下影响日棵间蒸发量的因素,在一年两熟地区保护性耕作条件下对影响蒸发的各因素进行田间试验研究,对10种保护性耕作模式的各参数与日棵间蒸发量的拟合关系进行分析。结果表明:8种耕作模式条件下日棵间蒸发量与叶面积指数、地表覆盖率有较好的三次函数关系,7种耕作模式下日棵间蒸发量与地表含水率具有较好的三次函数关系,3种耕作模式下日棵间蒸发量与地表温度具有三次函数关系。保护性耕作条件下日棵间蒸发量可近似用叶面积指数、地表覆盖率或者地表含水量计算。     

围封条件下贺兰山西坡植被恢复生态效益研究

研究围封2年后贺兰山西坡植被盖度、植被组成、地上草本生物量、地表枯落物量及枯落物持水力的变化特点。结果表明,围封2年后,贺兰山西坡北段、中段和南段的植被盖度分别增加了10.3%、8.2%、4.4%;围封对贺兰山西坡灌木物种组成影响较小,而对草本物种组成影响较大;中段的地上生物量比围封前增加了2.5倍,明显高于北段和南段,而围封对地表枯落物量的影响较小;就枯落物持水力来看,北段地表枯落物的涵养水源能力明显强于中段和南段。